ES2939339T3 - Composite electrode materials with improved structure - Google Patents

Abstract

The invention discloses structure-improved composite electrode materials. The composite electrode materials of this invention include at least one active material. The active material is coated with an artificial passive film on its surface to effectively prevent or reduce the contact of the electrolyte and the active material to avoid unnecessary consumption of lithium ions. In addition, they have a middle layer and an outer layer outside the artificial passive film. Both the middle layer and the outer layer are composed of the deformable electrolyte and the non-deformable electrolyte, but with different concentration ratios. Therefore, the best ion conduction is achieved with a lower resistance to charge transfer and a lower amount of organic solvent usage. (Automatic translation with Google Translate, without legal value)

Description

DESCRIPTION

Composite electrode materials with improved structure

BACKGROUND OF THE INVENTION CROSS REFERENCES TO RELATED APPLICATIONS

[0001] The present application claims priority to Taiwanese patent application 107139243 filed with the Taiwan Patent Office on November 6, 201.

field of invention

[0002] The present invention relates to electrode materials, in particular to structure-improved composite electrode materials adapted for a lithium-ion secondary battery system.

Related state of the art

[0003] Liquid electrolyte is often used for existing lithium ion secondary batteries as a means of transporting lithium ions. However, the volatile nature of the liquid electrolyte can negatively affect the human body and the environment. Furthermore, it is also a big safety issue for battery users due to the flammability of the liquid electrolyte.

[0004] Furthermore, one of the reasons for the destabilization of lithium batteries is the higher surface activity of the negative electrode and the higher voltage of the positive electrode. When the liquid electrolyte comes into direct contact with the electrodes, the interfaces between them are destabilized and the exothermic reaction occurs to form a passivation layer. These reactions would consume the liquid electrolyte and lithium ion and generate heat. When a local short circuit occurs, the local temperature rises rapidly. The passivation layer will become unstable and release heat. This exothermic reaction is cumulative by causing the temperature of the entire battery to continue to rise. One of the safety concerns of using a battery is that once the battery temperature rises to an initial temperature (activation temperature), thermal runaway starts leading to ignition or battery explosion. That is a major security issue for its use.

[0005] In recent years, solid electrolytes are a focus of research. The ionic conductivity of solid electrolytes is similar to the ionic conductivity of liquid electrolytes, without having the evaporation and combustion properties. Furthermore, the interfaces between solid electrolytes and the surface of active materials are relatively stable, either chemically or electrochemically. However, unlike the liquid electrolyte, the contact area between the solid electrolytes with the active materials is quite small, the contact surface is poor, and the charge transfer coefficient is low. Therefore, there is a problem that the charge transfer interface resistances of the active materials with the positive and negative electrodes are large. This is adverse for the efficient transmission of lithium ions. Therefore, it is still difficult to completely replace liquid electrolytes with solid electrolytes.

[0006] To solve the problems just mentioned, the Applicant provides composite electrode materials, such as those of US Application No. 16/253,928, constructed with different percentages of solid electrolyte and gel/gel electrolyte. liquid. Therefore, the best ionic conduction is achieved with a lower resistance to charge transfer and a reduced amount of organic solvent. However, if the amount of organic solvent can be further reduced, the safety and stability of the lithium battery would be greatly improved. US applications US2016/204427 A1 and US2014/287324 A1 refer to composite materials for electrodes comprising a core of active material coated with one or two layers, at least one of which comprises a solid electrolyte.

SUMMARY OF THE INVENTION

[0007] An objective of this invention is to provide composite electrode materials with an improved structure to overcome the above deficiencies. Artificial Passive Film (APF) is used to efficiently prevent liquid electrolytes from coming into contact with active materials. Therefore, unnecessary consumption of lithium ion and degradation of lithium battery can be avoided.

[0008] Furthermore, another object of this invention is to provide composite electrode materials with an improved structure that includes an intermediate layer and an outer layer constructed with different percentages of the dual-type electrolyte. Therefore, the problems of high resistance of charge transfer and small contact area caused by direct contact between the solid electrolyte and the active material are eliminated. The amount of organic solvents is reduced and battery safety is improved.

[0009] To implement the above, this invention discloses structure-improved composite electrode materials, including an active material, an artificial passive film, an intermediate layer, and an outer layer. The artificial passive film covers the active material, and the middle layer and outer layer cover the outside in sequence. Both the middle layer and the outer layer include a non-deformable electrolyte and a deformable electrolyte. The deformable electrolyte content is higher than the non-deformable electrolyte content of the intermediate layer. The content of the non-deformable electrolyte is greater than the content of the non-deformable electrolyte of the outer layer. The active material is coated with an artificial passive film on its surface to effectively block the contact of the electrolyte and the active material to prevent unnecessary consumption of lithium ion, which may lead to the degradation of the lithium battery. At the same time, the middle layer and the outer layer are formed with different concentration ratios. The amount of electrolytes in the gel/liquid is significantly reduced. In addition, the problems of high resistance of charge transfer and small contact area, caused by direct contact of the solid electrolyte and the active material, are eliminated. Therefore, the best ionic conduction is achieved with greater safety.

[0010] The further scope of applicability of the present invention will become apparent from the detailed description provided below. However, it is to be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are provided by way of illustration only, as various changes and modifications within the spirit and scope of the invention will become apparent to the those skilled in the art from this detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The present invention will be better understood from the detailed description provided below for illustrative purposes only and is therefore not limiting of the present invention, and wherein:

Figure 1 is a schematic diagram of the structure-improved composite electrode materials of this invention.

Figure 2 is a partially enlarged schematic diagram of the structure-improved composite electrode materials of this invention.

Figure 3 is a partially enlarged schematic diagram of another embodiment of the structure-improved composite electrode materials of this invention.

Figure 4 is a schematic diagram of structure-improved composite electrode materials adapted for a lithium battery of this invention.

Fig. 5 is a schematic diagram of another embodiment of structure-improved composite electrode materials adapted for a lithium battery of this invention.

DETAILED DESCRIPTION OF THE INVENTION

[0012] The invention provides composite electrode materials with an improved structure. The scope of the invention is defined by the appended claims. Both solid electrolytes and gel/liquid electrolytes have their own advantages and disadvantages. Today, it is still difficult to completely replace gel/liquid electrolytes with solid electrolytes. Therefore, a more suitable way is to mix with the solid electrolytes and gel/liquid electrolytes. The advantages of these two types of electrolytes are taken advantage of by the distribution configuration with different percentages, and the disadvantages of electrolytes are eliminated or minimized to achieve better ionic conduction. Furthermore, it is considered that the disadvantages of active materials and gel/liquid electrolytes would form a passive protective film. Artificial Passive Film (APF) is used to efficiently reduce or prevent gel/liquid electrolytes from coming into contact with active materials. The following is a description of the structure of the active material and the structure of the electrode.

[0013] See FIGS. 1-3, which are a schematic diagram of the structure-improved composite electrode materials of this invention, a partially enlarged schematic diagram of the structure-improved composite electrode materials of this invention, and a partially enlarged schematic diagram of another form embodiment of the structure-improved composite electrode materials of this invention. The composite electrode materials 10 of this invention include a plurality of active material 11, an intermediate layer 12, and an outer layer 13. An artificial passive film (APF) 101 is formed on the outer surface of the active material 11 and covers the active material. 11 to avoid or reduce contact of the gel/liquid electrolytes with the active material 11. Therefore, the artificial passive film (APF) 101 can be considered as an inner layer. The material of the APF 101 may be a non-solid electrolyte series or a solid electrolyte series based on lithium ion transfer or not. The thickness of APF 101 is substantially less than 100 nanometers. The series of non-solid electrolytes may be selected from the group consisting of conductive materials, non-lithium ceramic materials, and combinations thereof. Non-lithium ceramic materials can include zirconia, silica, alumina, titanium oxide, or gallium oxide. In addition, when the APF 101 is composed of non-lithium ceramic materials, the APF 101 may be formed by a deposition mechanical, physical/chemical deposition, or combinations of these. For mechanical deposition, a ball mill or a fluidized bed can be used. The thickness of the APF 101 is substantially less than 100 nanometers when the APF 101 is formed by mechanical deposition. Through physical/chemical deposition, the atomic scale stack-up film structure is formed. The thickness of the APF 101 can be substantially less than 20 nanometers. When the APF 101 is composed of conductive materials, the APF 101 can be formed by the same methods as mentioned above.

[0014] For such an APF 101 composed of the series of non-solid electrolytes, the additional electrolyte is necessary as a medium for transferring ions, in case the thickness of the APF 101 is larger. In case the thickness of the APF 101 is thinner, such as the atomic scale stacked film structure, the ion transfer could be performed directly.

[0015] The series of solid electrolytes may include oxide-based solid electrolytes, sulfide-based solid electrolytes, lithium aluminum alloy solid electrolytes, or lithium azide (LiNa) solid electrolytes, which may be crystalline or glassy. When the APF101 is selected from conductive materials, it may include a carbonaceous material (such as graphite or graphene) or a conductive polymer. In practice, the structure of FIG. 2 is better than the structure of FIG. 3. Furthermore, in FIG. 2, the APF 101 is preferably composed of a series of solid electrolytes.

[0016] Other illustrations of materials for the above solid electrolyte are described below. The solid sulfide-based electrolyte may be selected from one or more of the groups consisting of a glassy state of LÍ ² SP ² Ss, a crystalline state of Lix' My PSz' , and a glassy ceramic state of LÍ ² SP ² H.H.

where M is selected from one or more of the groups consisting of Si, Ge, and Sn;

x ’ 4y 5 = 2Z’ , 0 ^ y ^ 1 .

[0017] Preferably, the LÍ ² SP ² Ss glassy state may be selected from one or more of the groups consisting of 70LÍ2S-30P2S ^s glassy state, 75LÍ2S-25P2S ^s glassy state, and ^{8 0} LÍ ² glassy state S- ^{2 0} P ² S ^s . The LÍ ² SP ^{2 S s} glass-ceramic state may be selected from one or more of the groups consisting of 70LÍ2S-30P2Ss glass-ceramic state, 75LÍ2S-25P2Ss glass-ceramic state, and S ⁰ Li ² S- glass-ceramic state. ^{2 0} P ² S ⁵ . The crystalline state of Lix' My PSz' may be selected from one or more of the groups consisting of LiaPS4, Li4SnS4, Li4GeS4, L¡10SnP2S12, L¡10GeP4S12, LÍ1üSíP2S12, L¡10GeP2S12, Li/PaSn, Lg.54Sh.74P1 .44S11.7Cl0.3, p-LiaPS ⁴ , U ⁷ P ² SI, Li ⁷ PaSn, 0.4LiI-0.6Li4SnS4, and Li ⁶ PS ⁵ Cl.

[0018] The solid oxide-based electrolyte may be a solid oxide-based electrolyte with a fluorite structure. For example, it can be yttria stabilized zirconia (YSZ) with a mole fraction of 3 to 10%. The oxide-based solid electrolyte may be an ABO ³ oxide-based solid electrolyte, such as doped LaGaOa. Or, the solid oxide-based electrolyte can be Lh+x+y(Al, Ga)x (Ti, Ge) ² xSiyPa-yO ¹² , where 0^x^1 and 0^y^1. Also, the oxide-based solid electrolyte can be Li2O-Al20a-SiO2-P2O5-TiO2, Li ² O-AbOa-SiO ² -P ² O ⁵ -TiO ² -GeO ² , Naa.aZr1.7La0.aSiaPO12, Lia ^.5 Si ^0.5 P ^0.5 O ⁴ , LiaxLa ² /axTiOa, Li7LaaZr2O12, Li ⁰ .asLa ^0.56 Ti ^0.99 Al ^0.01 Oa, or Li ⁰ .a ⁴ LaTiO ^2.94 .

[0019] As mentioned above, depending on whether the ion passes through the APF 101 or not, the structure design of the APF can be as described below. The APF 101 can completely cover the active material 11, the APF 101 has pores to allow gel/liquid electrolytes to contact the surface of the active material 11, or the APF can form the above combinations.

[0020] See FIG. 2, for example: APF 101 essentially completely covers active material 11 to prevent gel/liquid electrolytes from coming into contact with active material 11. See FIG. a, for example: APF 101 has pores to allow gel/liquid electrolytes to flow through and lightly contact the surface of active material 11. APF 101 can be made up of a number of stacked powdered non-solid electrolytes. The stacked powder structure can form pores to reduce contact with the gel/liquid electrolytes and active material 11. Furthermore, based on the structure of FIG. a, The stacked powder structure would support the solid electrolyte interface (SEI) layer, which is formed on the surface of the active material 11, to increase chemical, electrochemical and thermal stability. Thus, cracking and rebuilding of the SEI layer can be avoided. In addition, the consumption of lithium ions can be decreased. In FIGS. 2-a, the thickness of the APF 101 is from several nanometers to tens of nanometers.

[0021] In the following paragraph, the intermediate layer 12 outside the APF 101 and the outer layer 1a outside the intermediate layer 12 are described. In order to facilitate the understanding of the structure, the manufacturing process of an electrode is first described . Generally speaking, the electrode 10 is mixed with the active material 11, a conductive material, a binder, and the gel/liquid electrolyte including the organic solvent and lithium salt. In this invention, the APF 101 is formed on the surface of the active material 11. The active material 11 with the APF 101 is mixed with the conductive material, the binder, and the gel/liquid electrolyte including the organic solvent and salt of lithium. Then, the gel/liquid electrolyte is extracted to obtain a first volume M1 of the gel/liquid electrolyte. After mixing the active material 11 with the conductive material and the binder, there would be a large number of holes with different sizes between the conductive material, the binder and the active material, as a result of the particle sizes and material properties. In general, the largest holes would form or stack in the region where the slurry solvent dries between the active materials. The diameters of the largest holes are approximately greater than 500 nanometers, and/or the distance between the hole and the artificial passive film 101 is greater than 500 nanometers. The smallest holes would form in the regions where they are closest to the surface of the active material 11 and/or are mixed with more conductive and binder material. The diameters of the smallest holes are approximately less than 500 nanometers, and/or these holes, which are closer to the active material 11, are distributed from the outside of the artificial passive film 101 at 500 nanometers. In general, the total volume of the smaller holes is less than the total volume of the larger holes. Preferably, the total volume of the smaller holes is much less than the total volume of the larger holes.

[0022] The intermediate layer 12 includes a first deformable electrolyte 121 and a first non-deformable electrolyte 122. The outer layer 13 includes a second deformable electrolyte 131 and a second non-deformable electrolyte 132. Since the holes are to be filled with electrolytes, the electrolytes do not defined by the phase states of this invention to fill the hole spaces easily. In this invention, electrolytes are defined as deformable electrolyte and non-deformable electrolyte according to their hardness and compressibility. Non-deformable electrolyte is the hardest quality solid electrolyte, which would not deform based on the size or shape of the holes. Therefore, the non-deformable electrolyte can only be introduced loosely into the openings. The deformable electrolyte is liquid electrolyte, gel electrolyte or wax-like electrolyte, which can be deformed according to the size or shape of the holes. Therefore, the deformable electrolyte can be definitely introduced into the remaining space of the holes after filling them with the non-deformable electrolyte.

[0023] The larger holes or the holes furthest away from the active material 11 are filled with a greater amount or concentration of the second non-deformable electrolyte 132. The smaller holes or the holes closer to the active material 11 are filled with a lower amount or concentration of the first deformable electrolyte 122. Then, the first deformable electrolyte 121 and the second deformable electrolyte 131 are introduced according to the distances from the active material. When the first deformable electrolyte 121 and the second deformable electrolyte 131 are introduced, the soft solid electrolyte 1211 can be introduced first. Then, at least one of the electrolytes that can fill the gaps between the non-deformable electrolyte and the soft solid electrolyte is selected from ionic liquid, ionic liquid electrolyte, gel/liquid electrolyte 1212, or the combination of these. , see Figs. 2 and 3. Therefore, the used amount of the gel/liquid electrolyte is significantly reduced to avoid the dangers caused by the gel/liquid electrolyte. As shown in the figures, the first deformable electrolyte 121 of the intermediate layer 12 includes the soft solid electrolyte 1211 and the gel/liquid electrolyte 1212. The second deformable electrolyte 131 of the outer layer 13 includes a soft solid electrolyte and at least an electrolyte selected from an ionic liquid, an ionic liquid electrolyte, a gel/liquid electrolyte, or a combination thereof.

[0024] Thus, a second volume M2 of the deformable electrolyte is obtained. Therefore, the first non-deformable electrolyte 122 and the first deformable electrolyte 121 are introduced into the holes within the range of APF 101 to about 500 nanometers and/or the holes with a diameter less than 500 nanometers to form the intermediate layer 12. The second nondeformable electrolyte 132 and second deformable electrolyte 131 are introduced into holes with distances from APF 101 of greater than about 500 nanometers and/or holes with a diameter greater than 500 nanometers to form the outer layer 13. The active material 11 and the related distributions in these drawings, FIGS. 1-3, for example, are merely schematic and are not intended to limit the distribution of materials. Some holes are filled with the first non-deformable electrolyte 122 and the second non-deformable electrolyte 132 instead of the gel/liquid electrolytes. Thus, the second volume M2 will not be larger than the first volume M1. Also, a part of the volume in M2 comes from the soft solid electrolyte. Therefore, the used amount of the gel/liquid electrolyte can be significantly reduced. The first deformable electrolyte 121 and the second deformable electrolyte 131 are the same or different materials. The first non-deformable electrolyte 122 and the second non-deformable electrolyte 132 are the same or different materials.

[0025] Thus, the content of the first deformable electrolyte 121 is higher than the content of the first non-deformable electrolyte 122 in the intermediate layer 12. The content of the second non-deformable electrolyte 132 is higher than the content of the second deformable electrolyte 131 in the outer layer 13 It is unquestionable that both the intermediate layer 12 and the outer layer 13 include the conductive materials and the binder resulting from forming the electrode. In general, the volume content of the first deformable electrolyte 121 of the intermediate layer 12 is greater than 50% of the total volume content of the first deformable electrolyte 121 and the first non-deformable electrolyte 122 of the intermediate layer 12, preferably greater than 90% . The content by volume of the second non-deformable electrolyte 132 of the outer layer 13 is greater than 50% of the total volume content of the second non-deformable electrolyte 131, and the second non-deformable electrolyte 132 of the outer layer 13 is preferably greater than 90%. Therefore, both higher safety (by reducing the amount of gel/liquid electrolyte used) and better ionic conduction (by solving area problems) are achieved. small contact and poor contact surface between the solid electrolyte and the active material, and the lowest charge transfer coefficient).

[0026] Intermediate layer 12 is directly contacted with active material 11 (or APF 101) to transfer ions. If the intermediate layer 12 is mainly composed of the non-deformable electrolyte, it would face the same problems as the conventional technique, such as a smaller and poor contact surface between the solid electrolyte and the active material and the low charge transfer coefficient. Therefore, the intermediate layer 12 is mainly composed of the deformable electrolyte. The volume content of the first deformable electrolyte 121 is greater than the volume content of the first non-deformable electrolyte 122. The volume content of the first deformable electrolyte 121 of the intermediate layer 12 is greater than 50% of the total volume content of the first electrolyte deformable 121 and the first nondeformable electrolyte 122 of the intermediate layer 12, is preferably greater than 90%. It could offer better non-directional ionic conduction. Furthermore, the condition of the contact surface between the first deformable electrolyte 121 and the active material 11 (or the APF 101) is much better than the contact surface between the solid electrolyte and the active material. The charge transfer interface resistances are reduced. A distance between the intermediate layer 12 and the artificial passive film 101 does not exceed 500 nanometers, or the first deformable electrolyte 121 and the first non-deformable electrolyte 122 of the intermediate layer 12 are inserted into holes with a diameter of less than about 500 nanometers. Therefore, the thickness of the intermediate layer 12 does not exceed 500 nanometers.

[0027] A distance between the outer layer 13 and the artificial passive film 101 is greater than 500 nanometers, or the second deformable electrolyte 131 and the second non-deformable electrolyte 132 of the outer layer 13 are inserted into holes with a diameter greater than about 500 nanometers. Therefore, the outer layer 13 is mainly composed of the non-deformable electrolyte. The volume content of the second non-deformable electrolyte 132 of the outer layer 13 is greater than 50% of the total volume content of the second non-deformable electrolyte 131 and the second non-deformable electrolyte 132 of the outer layer 13, preferably greater than 90%. The amount of organic solvent (the gel/liquid electrolyte) used is reduced to achieve better thermal performance and maintain safety. In the outer layer 13, the direction of ionic conduction is determined by the contact with the non-deformable electrolyte of particles of the solid electrolyte. Therefore, ion conduction is in a specific direction to allow lithium ions to perform high-speed, bulk transport.

[0028] The first non-deformable electrolyte 122 of the intermediate layer 12 and the second non-deformable electrolyte 132 of the outer layer 13 are selected from among a hard solid electrolyte, such as an oxide-based solid electrolyte, a lithium azide solid electrolyte ( LiNa) or a lithium aluminum alloy solid electrolyte, wherein the oxide-based solid electrolyte may be a lithium aluminum titanium phosphate (LATP) electrolyte. The first deformable electrolyte 121 of the intermediate layer 12 and the second deformable electrolyte 131 of the outer layer 13 may include an ionic liquid, an ionic liquid electrolyte, a gel/liquid electrolyte, or a soft solid electrolyte, wherein the soft solid electrolyte is selects from a sulfide based solid electrolyte, a hydride solid electrolyte or a polymer solid electrolyte. Solid polymer electrolyte includes polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), and polyvinyl chloride (PVC).

[0029] To further reduce the used amount of the organic solvent, the first deformable electrolyte 121 of the intermediate layer 12 and the second deformable electrolyte 131 of the outer layer 13 may mainly include the ionic liquid, the ionic liquid electrolyte or the solid electrolyte. soft. In other words, the main composition of the first deformable electrolyte 121 and the second deformable electrolyte 131 is ionic liquid, ionic liquid electrolyte, soft solid electrolyte, or a combination thereof. The gel/liquid electrolyte ratio is reduced.

[0030] Of course, the remaining non-deformable or deformable electrolytes can also be used, which have not been listed in detail. The above list is merely illustrative and is not intended to limit the invention to the above non-deformable or deformable electrolytes.

[0031] Practically applied to battery systems, the composite electrode materials 10 of this invention can serve as an electrode, such as a positive electrode. As can be seen in FIG. 4, the composite electrode materials 10, another electrode 30, the separator 42 and two current collectors 41, 43 form the battery system. Furthermore, the two electrodes, the positive electrode and the negative electrode, can use the composite electrode materials 10 of this invention, see FIG. 5.

[0032] Accordingly, in this invention, artificial passive film (APF) is used to effectively prevent or reduce contact of gel/liquid electrolytes with active materials. Therefore, unnecessary consumption of lithium ion and degradation of lithium battery can be avoided. Furthermore, the intermediate layer and the outer layer are built with different percentages of non-deformable electrolyte and deformable electrolyte. Therefore, the outer layer can allow lithium ions to be transferred at a high speed, and the middle layer offers non-directional ion conduction. Therefore, better ionic conduction is achieved. Besides, the The amount of organic solvent (the gel/liquid electrolyte) used is reduced to achieve better thermal performance and maintain safety. And if the proportion of the ionic liquid or the ionic liquid electrolyte is increased, the amount of organic solvent can be further reduced. In addition, the dual electrolyte system, with the non-deformable electrolyte and the deformable electrolyte, can effectively increase the ionic conduction. Especially, when the non-deformable electrolyte is the solid oxide-based electrolyte, the high chemical stability is maintained. Furthermore, the ionic conductivity and compatibility of the electrodes are increased through this dual electrolyte system.

Claims (8)

1. Structure-improved composite electrode materials adapted for a lithium-ion secondary battery system, comprising: an active material; an artificial passive film covering the active material; an intermediate layer, which covers the artificial passive film, wherein the intermediate layer includes a first non-deformable electrolyte and a first non-deformable electrolyte, wherein the volume content of the first non-deformable electrolyte is greater than the volume content of the first non-deformable electrolyte; and an outer layer, covering the intermediate layer, where the outer layer includes a second non-deformable electrolyte and a second non-deformable electrolyte, wherein the volume content of the second non-deformable electrolyte is greater than the volume content of the second deformable electrolyte; wherein the first deformable electrolyte in the middle layer and the second deformable electrolyte in the outer layer are composed of a soft solid electrolyte selected from a sulfide-based solid electrolyte, a hydride solid electrolyte, or a polymer solid electrolyte, and at least one electrolyte selected from an ionic liquid, an ionic liquid electrolyte, a gel or liquid electrolyte, or a combination thereof; where the thickness of the artificial passive film is less than 100 nanometers and completely covers the active material, where the artificial passive film is composed of a solid electrolyte, selected from oxide-based solid electrolyte, sulfide-based solid electrolyte, electrolyte solid lithium aluminum alloy or solid lithium azide (LiNa) electrolyte, or where the artificial passive film is a non-solid electrolyte, selected from the group consisting of conductive materials, non-lithium ceramic materials, and combinations thereof, where the materials conductors include a carbonaceous material or a conductive polymer, and lithium-free ceramic materials include zirconia, silica, alumina, titanium oxide or gallium oxide; where the distance between the interlayer and the artificial passive film does not exceed 500 nanometers; where the distance between the outer layer and the artificial passive film is greater than 500 nanometers; wherein the volume content of the first deformable electrolyte of the intermediate layer is greater than 50% of the total volume content of the first deformable electrolyte and the first non-deformable electrolyte of the intermediate layer; wherein the volume content of the second non-deformable electrolyte of the outer layer is greater than 50% of the total volume content of the second deformable electrolyte and the second non-deformable electrolyte of the outer layer; wherein the first non-deformable electrolyte of the intermediate layer and the second non-deformable electrolyte of the outer layer are selected from among an oxide-based solid electrolyte, a lithium azide (LiNa) solid electrolyte or a lithium-aluminum alloy solid electrolyte . The structure-improved composite electrode materials of claim 1, wherein the first intermediate layer non-deformable electrolyte and the outer layer second non-deformable electrolyte are crystalline or glassy solid electrolytes. The structure-improved composite electrode materials of claim 1, wherein the volume content of the first deformable electrolyte in the intermediate layer is greater than 90% of the total volume content of the first deformable electrolyte and the first non-deformable electrolyte in the intermediate layer. . The structure-improved composite electrode materials of claim 1, wherein the volume content of the second non-deformable electrolyte of the outer layer is greater than 90% of the total volume content of the second deformable electrolyte and the second non-deformable electrolyte of the outer layer. . The structure-improved composite electrode materials of claim 1, wherein the composite electrode materials serve as a positive and/or negative electrode of a lithium battery. The structure-improved composite electrode materials of claim 1, wherein the first deformable electrolyte and first non-deformable electrolyte of the intermediate layer are introduced into holes with a diameter of less than about 500 nanometers, and the second deformable electrolyte and second electrolyte non-deformable outer layer are inserted into holes with a diameter greater than approximately 500 nanometers. The structure-improved composite electrode materials of claim 1, wherein the solid oxide-based electrolyte is a lithium aluminum titanium phosphate (LATP) electrolyte. The structure-improved composite electrode materials of claim 1, wherein the polymeric solid electrolyte includes polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), and polyvinyl chloride (PVC). .